Graphene-based structure, method of suspending graphene membrane, and method of depositing material onto graphene membrane

ABSTRACT

An embodiment of a method of suspending a graphene membrane on a support structure includes attaching graphene to a substrate. A pre-fabricated support structure having the gap is attached to the graphene. The graphene and the pre-fabricated support structure are then separated from the substrate which leaves the graphene membrane suspended on the pre-fabricated support structure. An embodiment of a method of depositing material includes placing a support structure having a suspended graphene membrane under vacuum. A precursor is adsorbed to a surface of the graphene membrane. A portion of the graphene membrane is exposed to a focused electron beam which deposits a material from the precursor onto the graphene membrane. An embodiment of a graphene-based structure includes a support structure having a gap, a graphene membrane suspended across the gap, and a material deposited in a pattern on the graphene membrane.

RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. NonProvisional application Ser. No. 12/409,938, filed Mar. 24, 2009, whichin turn claims priority to and the benefit of U.S. ProvisionalApplication 61/039,002, filed on Mar. 24, 2008, both of whichapplications are hereby incorporated by reference.

STATEMENT OF GOVERNMENTAL SUPPORT

This invention was made with government support under Contract No.DE-AC02-05CH11231 awarded by the U.S. Department of Energy. Thegovernment has certain rights in this invention.

FIELD OF THE INVENTION

This invention relates generally to graphene.

BACKGROUND OF THE INVENTION

Graphene is a single planar sheet of sp3-bonded carbon atoms that aredensely packed in a honeycomb crystal lattice and which was firstisolated in 2004. The carbon-carbon bond length in graphene isapproximately 1.42 Å. Since the experimental verification the followingyear of many of its theoretically predicted electronic properties,single- and few-layer graphene has been suggested as a promisingcandidate material for future microelectronic devices. Graphene is inmany respects similar to carbon nanotubes, but expectations are that forvarious applications graphene will be easier to control. This is partlybecause it can be patterned into arbitrary shapes by lithographic meanswhich readily provides a degree of control difficult to achieve withnanotubes.

Nevertheless, smaller devices require not only novel materials but alsoa means of shaping those materials into a tiny circuit. State of theart, resist based, electron beam lithography (EBL) methods,notwithstanding throughput issues, rarely achieve a half-pitch of lessthan 20 nm on hulk substrates. Smaller features, if created by EBL, arein most cases of a special shape, e.g., an isolated line. It has beenargued that resist-based EBL on a substrate is inherently limited toaround 20 nm half-pitch for periodic patterns. Although electron beamscan be focused to sub-angstrom diameters, scattered and secondaryelectrons generated in a bulk substrate and resist limit the modulationin the energy profile that can ultimately realized. Accordingly, thesmallest feature sizes using EBL having not improved significantly overthe last three decades.

On bulk substrate, the spatial resolution of electron-beam induceddeposition (EBID) and also of convention lithography is limited byscattered and secondary electrons, with a minimum half pitch of around20 nm. Good resolution has been achieved by EBID ultrathin amorphouscarbon and silicon nitride membranes (see, e.g., van Dorp, W. F., etal., One nanometer structure fabrication using electron beam induceddeposition, Microelectronic Eng., 83, 1468-1470 (2006)).

An existing technique for producing a suspended graphene membrane istaught in Meyer, J. C., et al., The structure of suspended graphenesheets, Nature, 446, 60-63 and in the supplementary information to thispublication (doi:10.1038/nature05545). In this technique, grapheneflakes are placed on an oxidized surface of a silicon wafer upon which ametal grid is produced by deposition of a metal, electron beamlithography, and etching.

Graphene holds potential for novel electronic, thermal and mechanicaldevices. Many devices currently made use graphene adhered to asubstrate. However, for many potential applications, a suspendedmembrane of graphene is essential, such as for nanoetectromechanicaldevices. While there is the existing technique for producing suspendedgraphene that is discussed above, it is complicated and consequentlyexpensive. A more efficient and less expensive technique is desirable.Further, graphene is useful for many devices as it has a highconductivity and is sensitive to “gating”. However, a new form oflithography is needed to make extremely small devices on graphene.

SUMMARY OF THE INVENTION

An embodiment of a method of suspending a graphene membrane across a gapin a support structure of the present invention includes attachinggraphene to a substrate. A pre-fabricated support structure having thegap is attached to the graphene. The graphene and the pre-fabricatedsupport structure are then separated from the substrate which leaves thegraphene membrane suspended across the gap in the pre-fabricated supportstructure. In an embodiment, the method includes separating the graphenefrom bulk graphite prior to attaching the graphene to the substrate.

According to an embodiment, attaching the pre-fabricated supportstructure includes placing a pre-fabricated support structure having thegap on the graphene; immersing the pre-fabricated support structure andthe graphene in a solvent, and evaporating the solvent which attachesthe pre-fabricated support structure to the graphene.

According to an embodiment, the graphene is attached to a sacrificialsurface of the substrate. The graphene and the pre-fabricated supportstructure may be separated from the substrate by etching the sacrificialsurface, which may be accomplished by immersing the sacrificial surfaceand the graphene in an etch solution. In an embodiment, the sacrificialsurface includes silicon dioxide. For this embodiment, the etch solutionincludes potassium hydroxide or another suitable solvent, in anotherembodiment, the sacrificial surface includes polymethyl methacrylate andthe etch solution includes an organic solvent. The organic solvent maybe selected from acetone, methylpyrrolidone, or another suitablesolvent.

According to an embodiment, separating the graphene and thepre-fabricated support structure from the substrate includes placing asolvent adjacent to an edge of the pre-fabricated support structure. Thesolvent expands beneath the pre-fabricated support structure and thegraphene, which causes the pre-fabricated support structure with thegraphene membrane suspended across the gap to release from thesubstrate.

According to an embodiment, attaching the pre-fabricated supportstructure to the graphene includes applying an adhesive to a surface ofthe pre-fabricated support structure and bringing the adhesive intocontact with the graphene. In such an embodiment, the graphene and thepre-fabricated support structure may be separated from the substrate bypulling the pre-fabricated support structure away from the substrate,which leaves the graphene attached to the pre-fabricated supportstructure by the adhesive. This embodiment may include immersing thegraphene and the pre-fabricated support structure in a solvent to removeexcess adhesive.

According to an embodiment, the method may further include heating thepre-fabricated support structure having the graphene membrane suspendedacross the gap after separating the pre-fabricated support structure andthe graphene membrane from the substrate.

According to embodiments, the pre-fabricated support structure may be aTEM (transmission electron microscopy) grid. According to an embodiment,the pre-fabricated support structure may include a plurality of gaps. Insuch an embodiment, separating the graphene and the pre-fabricatedsupport structure from the substrate may leave the graphene membranesuspended across at least two of the gaps in the pre-fabricated supportstructure. According to an embodiment, attaching the pre-fabricatedsupport structure to the graphene includes attaching the pre-fabricatedsupport structure to the substrate beyond where the pre-fabricatedsupport structure attaches to the graphene.

An embodiment of a method of depositing material of the presentinvention includes placing a support structure having a graphenemembrane suspended across a gap under vacuum. A precursor is adsorbed toa surface of the graphene membrane. A portion of the graphene membraneis exposed to a focused electron beam which deposits a material from theprecursor onto the graphene membrane.

According to embodiments, adsorbing the precursor to the surface of thegraphene membrane may take place prior to, while, or after placing thesupport structure having the graphene membrane under the vacuum.

According to an embodiment, exposing the portion of the graphenemembrane to the focused electron beam causes amorphous carbon to bedeposited onto the graphene membrane. According to another embodiment,exposing the portion of the graphene membrane to the focused electronbeam causes a dopant to be deposited onto the graphene membrane.

According to an embodiment, the method of depositing the materialfurther includes raster scanning the electron beam across the graphenemembrane to produce a pattern of the material on the graphene membrane.In an embodiment, the pattern forms an electronic device on the graphenemembrane. In another embodiment, the pattern forms a plurality of localperturbations on a nanometer scale on the graphene membrane. In yetanother embodiment, the pattern forms an etch mask for furtherprocessing of the graphene membrane.

An embodiment of a graphene-based structure of the present inventionincludes a support structure having a gap, a graphene membrane suspendedacross the gap, and a material deposited in a pattern on the graphenemembrane. In an embodiment, the material includes carbon. In anembodiment, the pattern comprises a feature dimension of less than about2.5 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and others will be readily appreciated by theskilled artisan from the following description of illustrativeembodiments when read in conjunction with the accompanying drawings.

FIG. 1 provides optical microscopy images taken in the course ofpreparation of a suspended graphene membrane. Panel (a): Opticalmicrograph of a flake on a Si/SiO2 substrate. Panel (b): Quantifoil™grid on top of the graphene flake, immersed in isopropanol. Color ringsappear just before the liquid is completely evaporated as the perforatedcarbon film is pulled into contact with the surface. Panel (c):Quantifoil™ (with perforated carbon film) on the graphene flake. Panel(d): Free hanging flake (low-magnification TEM image) after release fromthe substrate. Spacing (period) of the holes is 2.5 μm. The dashed-linecircles in Panels (a) and (d) indicate the single-layer region of thissample. Scale bars are (a) 2 μm, (b) and (c) 10 μm, and (d) 5 μm.

FIG. 2 provides electron microscopy images taken of a graphene membrane.Panel (a): A free-standing membrane spanning a 1.3 μm hole in a TEMgrid. Panel (b): The same membrane after electron-beam induceddeposition of a dot array on part of the area. Panel (c): LawrenceBerkeley National Laboratory logo written onto graphene. Panel (d):Pattern with 2.5 nm half pitch (5 nm dot separation). Panel (e): Linesin the logo (windows of the clock tower at top right) spaced 10 nmapart. Panel (I): Intensity profile of the electron beam that was usedto write these structures. Scale bars are (b) and (c) 100 nm, and (d) 20nm.

FIG. 3 provides a TEM image of the smallest points written on a graphenemembrane by a focused electron beam.

FIG. 4 provides TEM images of a graphene membrane. (a) Low magnificationoverview image of a suspended graphene sheet on the perforated carbonfoil. (b) High resolution close-up of a graphene membrane. We observesmall, extremely clean areas with diameters of ten to fifty nanometerswhere no contrast is visible, separated by regions with thin amorphousadsorbates. Scale bars are (a) 1 μm and (b) 10 nm.

FIG. 5 provides adatom images. (a) Carbon adatom (black arrow). (b)Intensity profiles from several images of the carbon adatom (black), anda simulated profile (red). Inset in (b) shows the simulated image. (c)Carbon adatom configuration (according to Nordlund et al., Formation ofion irradiation induced small-scale defects on graphite surfaces, Phys.Rev. Lett., 77, 699 (1996)). (d) Hydrogen adatoms on the same sample(dark grey spots), a selection of which are indicated by a red arrow.The profile plots are shown in (e). Black arrow in (d) is again thecarbon adatom. Red line in (e) is the simulated profile for a hydrogenadatom. (f) Configuration of a chemisorbed hydrogen atom (according toJeloaica and Sidis, DFT investigation of the adsorption of atomichydrogen on a cluster-model graphite surface, Chem. Phys. Lett., 300,157 (1999)). All scale bars are 2 nm.

FIG. 6 provides TEM images showing dynamics of defects, (a-c) Generationof vacancies due to electron irradiation. Time between (a) and (c) is 50minutes. (d-f) Annealing of a vacancy by interaction with an adsorbate.We observe two individual vacancies (d), and then (e) trapping of alarger adsorbate, corresponding to a mass of a few carbon atoms, on oneof the defects. After ca. 5 minutes, both the adsorbate and the onevacancy disappear (f), showing that the missing carbon atom in thegraphene sheet has been replaced by an atom from the adsorbate. Scalebar is 2 nm.

FIG. 7 provides TEM images showing molecular scale adsorbates. (a)Molecule suspended between other adsorbates (arrow). (b-d) Migration ofa carbon chain, where one end remains attached in each step. Thecontrast is in agreement with an alkane molecule. Scale bar is 2 nm.

DETAILED DESCRIPTION

Before the present invention is described, it is to be understood thatthis invention is not limited to particular embodiments described, assuch may, of course, vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting, since the scope ofthe present invention will be limited only by the appended claims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimits of that range is also specifically disclosed. Each smaller rangebetween any stated value or intervening value in a stated range and anyother stated or intervening value in that stated range is encompassedwithin the invention. The upper and lower limits of these smaller rangesmay independently be included or excluded in the range, and each rangewhere either, neither or both limits are included in the smaller rangesis also encompassed within the invention, subject to any specificallyexcluded limit in the stated range. Where the stated range includes oneor both of the limits, ranges excluding either or both of those includedlimits are also included in the invention.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present invention, the preferred methodsand materials are now described. All publications mentioned herein areincorporated herein by reference to disclose and describe the methodsand/or materials in connection with which the publications are cited.

It must be noted that as used herein and in the appended claims, thesingular forms “a”, “and”, and “the” include plural referents unless thecontext clearly dictates otherwise. Thus, for example, reference to “amembrane” includes a plurality of such membranes, and so forth.

These and other objects, advantages, and features of the invention willbecome apparent to those persons skilled in the an upon reading thedetails of the invention as more fully described below.

Electron-Beam Induced Deposition on Graphene Membranes

The invention provides a method of preparing a suspended graphenemembrane. The method is compatible with various processing methods, andtransmission electron microscopy (TEM). Graphene is first provided on asilicon substrate with a silicon dioxide layer. Then a grid material,such as a Quantifoil™ electron microscopy grid, is placed on thegraphene and immersed in a solvent. As the solvent evaporates, the gridis pulled into close contact with the substrate and the graphenemembrane. The contact between the Quantifoil™ grid and the graphenemembrane can be further improved by heating the sample.

The present invention also provides a graphene-based structurecomprising a graphene membrane and a material in a pattern, where thepattern may have a resolution of less than about 2.5 nm on saidgraphene. In some embodiments, the resolution is 2.0 nm or less, 1.5 nmor less, or 1.0 nm or less. The deposited material can be amorphouscarbon. The deposited material can be produced using any suitable means,such as using a focused electron beam. A focused electron beam can bescanned across the graphene and causes the deposition of amorphouscarbon. This effect is known as electron-beam induced deposition (EBID).

In contrast to amorphous thin films, graphene has interesting electronicproperties that can be significantly altered directly by doping, shapingor defect generation. By using graphene membranes, one skilled in theart can directly pattern the material for next generation of electronicdevices. Doping patterns can be deposited ion order to define electroniccircuits by a suitable choice of precursor for EBID. Also, the arbitrarydesign of local perturbations with nanometer precision allows for thescattering and diffraction of relativistic quasiparticles, since theelectron wavelength in graphene is comparable to the spacing of thedots. This leads to novel electronic and thermal devices with directapplications in the electronics.

In some embodiments, a simple periodic superlattice leads to a gap inthe density of states. More elaborate patterns can be designed aswaveguides or to obtain localized states. Local changes in theelectronic properties around or within a controlled pattern of defectscan be explored by scanning electron microscopy or scanning tunnelingmicroscopy. In addition, the deposited carbon on the graphene membranecan serve as an etch mask or for data storage.

The present invention provides for a direct-write deposition method forarbitrary patterns on suspended graphene membranes with a resolution(half-pitch) of 2.5 nm or less. These patterns can serve as an etchmask, or to create a doping pattern. In addition, the arbitrary designof local perturbations with nanometer precision can allow a wide rangeof experiments that explore the scattering and diffraction ofrelativistic quasiparticles. The invention provides for a novel, simpleand efficient process to obtain a free-standing graphene membrane, andfor a method to facilitate the high-resolution patterning of such afree-standing graphene membrane.

The resolution restrictions of EBL from profile broadening on a bulksubstrate have been explored previously by electron-beam induceddeposition (EBID) on ultra-thin substrates. In particular, electron-beaminduced deposition with small feature sizes has been previouslydemonstrated on amorphous carbon films and silicon nitride membraneswith a thickness of 10 nm and 30 nm, respectively. It has also beendemonstrated that a range of materials other than amorphous carbon canbe deposited by careful control of the precursor. In fact, calculationsshow that high resolution should be possible by MID on any thickness ofsubstrate; however, the tails of deposited spots (deposited materialoutside of the beam) is suppressed on ultra-thin membranes. Themembranes of the present invention are another one to two orders ofmagnitude thinner than previously studied membranes, thereby reducingthe effects of secondary and scattered electrons even further. Indeed,the minimum feature size of the membranes of the present inventioncorresponds to the diameter of the focused electron beam, and nodeposition is observed outside the deposited structures.

An important difference between using an amorphous film substrate, andgraphene, for patterning is that graphene has remarkable electronicproperties that can be significantly altered directly by doping, shapingor defect generation. A graphene membrane can be directly patternedusing the deposition method of the present invention to produce a hostof next generation electronic devices.

Method of Suspending the Graphene Membrane

The present invention provides for a method of suspending a graphenemembrane from a support structure. The method comprises first providinggraphene, such as a graphene flake made by the well-known “scotch tape”method. The graphene is transferred to a substrate or solid supportcomprising one or more holes, openings or perforations, such as anelectron microscopy grid. A suitable electron microscopy grid is acommercially available electron microscopy grid, such as a Quantifoil™200 Mesh gold grids with 1.3 μm holes in the carbon film.

In some embodiments of the method, the graphene provided is a grapheneflake on a silicon substrate with a 300 nm thick silicon dioxide layer.The graphene flake can be identified by optical microscopy. AQuantifoil™ grid is placed on the flake. A small drop of a suitablesolvent, such as an organic solvent as isopropanol, is added to theflake and allowed to completely evaporate. The surface tension of thesolvent during evaporation pulls the perforated carbon film into contactwith the substrate (or solid support) and the graphene flake. Theadhesion of the flake to the substrate or solid support can be improvedby heating the flake, such as to a temperature of about 200° C. for 5minutes. Heating can be by any suitable means, such as a hot plate. Theflake is then allowed to cool. After cooling, the substrate with the nowwell-sticking TEM grid into a 30% solution of semiconductor gradepotassium hydroxide at room temperature. The silicon dioxide layer isslowly etched by the potassium hydroxide, and the TEM grid along withthe graphene sheets falls off after a time ranging from a few minutes toa few hours. It is then transferred, without drying, into a water bath,and subsequently to isopropanol. Finally, the sample is carefully driedin air. The single- and few-layer graphene sheets remain suspendedacross the holes of the Quantifoil™ grid.

In other embodiments of the method, the graphene flakes prepared on asilicon substrate with a 300 nm thick silicon dioxide layer and a 10-30nm layer of a suitable acrylate, such as polymethylmetacrylate (PMMA). AQuantifoil™ TEM grid is placed onto the flakes and pulled into contactwith the surface by evaporation of a suitable solvent, such as anorganic solvent, such as isopropanol. Contact between the flake and thegrid can be improved by heating on a hot plate. The top layer of thesubstrate is then dissolved in a bath of another suitable solvent, suchas an organic solvent, such as acetone or methylpyrrolidone. The TEMgrid with the graphene flake is then separated from the substrate. It iscan then be transferred to isopropanol again before drying. Thesemethods avoid the use of any acid or base (such as potassium hydroxide).

Just before insertion into a TEM, the graphene membrane samples areagain heated on a hot plate to reduce the amount of adsorbates that arepresent on the sample surface due to the wet preparation and due to airexposure. For the results shown here, samples were heated for 10 minutesat 200° C. This treatment reduces the rate of carbon deposition in EBID,which makes it easier to control at the expense of a longer writingtime.

Method of Depositing Carbon on the Graphene Having a Resolution of 2.5nm or Less

A JEOL 2010 Advanced High Performance TEM operated at 100 kV to writepatterns on a graphene membrane. A small beam is formed in theconvergent-beam diffraction mode of the illumination system, with a FWHMof 2.5 nm and a total current of approximately 1 pA (FIG. 2, Panel f).The advantage of using a TEM for this process is that the shape and sizeof the beam can be observed directly; however, we note that ananometer-sized beam can be generated with any high quality scanningelectron microscopy and lithography system as well. By employing acomputer controlled movement of the electron beam, arbitrary patternsare created. In contrast to the “digital” nature of resist basedlithography, we have here a continuous, “grayscale” control of thedeposited amount of material.

FIG. 2, Panels a and b show the same graphene membrane before and afterwriting a periodic dot array. FIG. 2, Panel c shows a different membranewith a non-periodic pattern, the logo of the Lawrence Berkeley NationalLaboratory. The windows of the clock tower on the right-most part of thepattern are spaced only 10 nm apart (FIG. 2, Panel e). A carbon patternobtained in this way is a dot array with a spacing of 5 nm (i.e. a halfpitch of 2.5 nm), as shown in FIG. 2, Panel d. Here, the dwell time ateach point was one second. The precursors in the EBID process arehydrocarbons adsorbed on the sample surface, as evidenced by the factthat the amount and time of heating the sample before insertion into theTEM strongly affects the deposition rate. The heating reduces the EBIDrate (increases write time) but makes it more controllable for smalleststructures.

The present invention also provides for method of detecting structureson a graphene membrane. This method is a tremendous advance inmicroscopy methods and can be used to detect and observe individualatoms, such as hydrogen atoms and carbon atoms, and individual smallmolecules, including their real-time dynamics, in a transmissionelectron microscope (TEM).

This method is derived not from building a better TEM, but rather byexploiting a new material configuration, a clean single-layer of asuspended graphene membrane, as a sample support membrane that, ineffect, is invisible in the TEM. Adatoms and other adsorbates on thissingle-atom-thick membrane can be seen as if they were suspended in freespace. Even hydrogen, the lightest element, is now easily imaged usingonly a modest-resolution TEM. The method can be reproduced in any basicmicroscopy laboratory in the world—no complex lithographic samplepreparation is needed.

This method can be applied in all areas of research and technologydevelopment where very small particles and individual molecules are tobe structurally identified, including nanomaterials, complex chemicals,or biological structures. This method also makes possible a study ofreal-time dynamics of such objects, with implications for examination ofatomic interactions, chemical reactions, and defect formation andhealing.

Applications of the Present Invention

The above results demonstrate a means to create arbitrary shapes onsingle- and few-layer graphene membranes with a resolution of 2.5nanometers with continuous control over the amount of depositedmaterial. This is a resolution that, by extrapolating from theinternational technology roadmap for semiconductors (ITRS), will be theDRAM half pitch in the year 2034. Indeed, if we consider the dots inFIG. 2, Panel d as bits for data storage, we have an extremely highinformation density per volume due to the ultrathin substrate: If theentire English Wikipedia (1 GB of text) were written onto graphene, thesheet could be folded or rolled into a cube with an edge length of only5 micrometers (taking into account a height of the dots of 5 nm). Unlikepatterns written by scanning tunneling microscopy atomic manipulationtechniques which exist only at cryogenic temperatures, these grapheneinformation patterns are stable at room temperature with an expectedlifetime of many thousands of years.

Given the high sensitivity of graphene's electronic properties tosmall-scale perturbations, our deposited material will have asignificant effect on the local electronic structure of the graphenemembrane. An individual deposited dot will thus act as a spatiallycontrolled scattering center. It is then easy to conceive of waveguideand optics analogies, e.g., a diffraction grating, for the chargecarrier waves. Indeed, the dimensions of our structures are well matchedto the wavelength of the electrons in graphene of ca. 4.26 nm. Weanticipate that the ability to create also non-periodic, arbitraryshapes will lead to a wide range of interesting experiments. Aspreviously mentioned, it has also been demonstrated that, by a suitablechoice of the precursor, a wide range of materials other than carbon canbe deposited by EBID. In this way, it should be possible to createspecific doping patterns on graphene, in addition, EBID-depositedamorphous carbon can be used as an etch mask, pointing to a way to “cutout” a pre-selected structure from a graphene sheet.

The suspended graphene membrane of the present invention is useful fornumerous applications. Such applications include, but are not limitedto, high-volume commercial products and specialized research toots, suchas electron microscopy support and further investigation into theproperties of graphene. The graphene membrane of the present inventioncan be used as a support in TEM imaging. Also, the present inventionprovides for a direct visualization of individualized carbon adatoms,vacancies, carbon chains and monolayer adsorbates and their dynamics ongraphene membranes by TEM. Using a single-layer graphene membrane, thereis no background signal at all from the support membrane and adsorbatescan be seen as if they were suspended in free space. One can study thedynamics of individual adatoms, vacancies, larger adsorbates as well asthe formation of nanometer-sized holes in the electron beam. Graphenemembranes provide a means to study the dynamics of chemical reactions oridentify the structure of unknown adsorbates with potentially atomicresolution. In addition, the study of atomic scale defects and edges ingraphene layers may provide insights on how to alter their electronicproperties.

The suspended graphene membranes is particularly useful fornanoelectromechanical systems (NEMS) applications. The suspendedgraphene membranes can serve as sensitive chemical detectors, as part ofa tuned electromechanical circuit and filter, as a basis fornanoelectronics or nanothermal devices, or the like.

The electron-beam induced deposition on graphene of the presentinvention can be used to create nanometer-scale doping patterns,diffraction gratings, or etch masks in this novel electronic material.

The invention having been described, the following examples are offeredto illustrate the subject invention by way of illustration, not by wayof limitation.

Example 1 Method of Suspending a Graphene Membrane

Our experimental procedure begins with graphene flakes made by theestablished “scotch tape” method. In order to suspend graphenemembranes, we have developed transfer processes of the graphene flakesto commercially available electron microscopy grids (Quantifoil 200 Meshgold grids with 1.3 μm holes in the carbon film). In the first method,we start with graphene flakes on a silicon substrate with a 300 nmsilicon dioxide layer. We identify graphene flakes by optical microscopy(FIG. 1, Panel a), and place the Quantifoil grid onto the flake. A smalldrop of isopropanol is added (FIG. 1, Panel b) and left to evaporate.The surface tension of this solvent during evaporation pulls theperforated carbon film into contact with the substrate and grapheneflakes (FIG. 1, Panel c). To improve the adhesion, we now heat thesample on a hot plate at 200° C. for 5 minutes. After cooling, we placethe substrate with the now well-sticking TEM grid into a 30% solution ofsemiconductor grade potassium hydroxide at room temperature. The silicondioxide layer is slowly etched by the potassium hydroxide, and the TEMgrid along with the graphene sheets falls off after a time ranging froma few minutes to a few hours. It is then transferred, without drying,into a water bath, and subsequently to isopropanol. Finally, the sampleis carefully dried in air. The single- and few-layer graphene membranesremain suspended across the holes of the Quantifoil grid.

Example 2 Method of Suspending a Graphene Membrane

In another method, we begin with graphene flakes prepared on siliconsubstrates with a 300 nm silicon dioxide layer and a 10-30 nm layer ofpolymethylmetacrylate (PMMA). Again, the Quantifoil TEM grid is placedonto the flakes and pulled into contact with the surface by evaporationof a solvent (isopropanol). Contact is improved by heating on a hotplate. The top layer of the substrate is now dissolved in a bath ofacetone or methylpyrrolidone. After separating the TEM grid with thegraphene flakes from die substrate, it is again transferred toisopropanol before drying. This second method avoids the use of acids orbases (such as potassium hydroxide).

Just before insertion into the TEM, the graphene membrane samples areagain heated on a hot plate to reduce the amount of adsorbates that arepresent on the sample surface due to the wet preparation and due to airexposure. For the results shown here, samples were heated for 10 minutesat 200° C. We clearly observe that this treatment reduces the rate ofcarbon deposition in EBID, which makes it easier to control at theexpense of a longer writing time.

We use a JEOL 2010 TEM operated at 100 kV to write the patterns. A smallbeam is formed in the convergent-beam diffraction mode of theillumination system, with a FWHM of 2.5 nm and a total current ofapproximately 1 pA (FIG. 2, Panel f). The advantage of using a TEM forthis process is that the shape and size of the beam can be observeddirectly; however, we note that a nanometer-sized beam can be generatedwith any high quality scanning electron microscopy and lithographysystem as well. By employing a computer controlled movement of theelectron beam, arbitrary patterns are created. In contrast to the“digital” nature of resist based lithography, we have here a continuous,“grayscale” control of the deposited amount of material.

FIG. 2, Panels a and b show the same graphene membrane before and afterwriting a periodic dot array. FIG. 2, Panel c shows a different membranewith a non-periodic pattern, the logo of the Lawrence Berkeley NationalLaboratory. The windows of the clock tower on the right-most part of thepattern are spaced only 10 nm apart (FIG. 2, Panel e). The smallestcarbon pattern we obtained in this way is a dot array with a spacing of5 nm (i.e. a half pitch of 2.5 nm), as shown in FIG. 2, Panel d. Here,the dwell time at each point was one second. The precursors in the EBIDprocess are hydrocarbons adsorbed on the sample surface, as evidenced bythe fact that the amount and time of heating the sample before insertioninto the TEM strongly affects the deposition rate. The heating reducesthe EBID rate (increases write time) but makes it more controllable forsmallest structures.

The above results demonstrate a means to create arbitrary shapes onsingle- and few-layer graphene membranes with a resolution of 2.5nanometers with continuous control over the amount of depositedmaterial.

Example 3 Imaging and Dynamics of Carbon and Hydrogen Atoms on Graphene

Observing the individual building blocks of matter is one of the primarygoals of microscopy. The invention of the scanning tunneling microscoperevolutionized experimental surface science in that atomic-scalefeatures on a solid-state surface could finally be readily imaged.However, scanning tunneling microscopy has limited applicability due torestrictions, for example, in sample conductivity, cleanliness, and dataacquisition rate. An older microscopy technique that of transmissionelectron microscopy (TEM) has benefited tremendously in recent yearsfrom subtle instrumentation advances, and individual heavy (high atomicnumber) atoms can now be detected by TEM even when embedded within asemiconductor material. However, detecting an individual low atomicnumber atom, for example carbon or even hydrogen, is still extremelychallenging, if not impossible, via conventional TEM due to the very lowcontrast of light elements. Here we demonstrate a means to observe, byconventional transmission electron microscopy, even the smallest atomsand molecules: On a clean single-layer graphene membrane, adsorbatessuch as atomic hydrogen and carbon can be seen as if they were suspendedin free space. We directly image such individual adatoms, along withcarbon chains and vacancies, and investigate their dynamics in realtime. These techniques open a way to reveal dynamics of more complexchemical reactions or identify the atomic-scale structure of unknownadsorbates. In addition, the study of atomic scale defects in graphenemay provide insights for nanoelectronic applications of this interestingmaterial.

The atomic-scale resolution of TEM comes at the price of requiring thatthe transmitted electron beam reach the imaging lenses and detector, andtherefore TEM works only for ultra thin, electron transparent samples.In high-resolution transmission electron microscopy (HRTEM) and allrelated techniques such as electron diffraction, scanning transmissionelectron microscopy (STEM), electron energy loss spectroscopy, orelemental mapping, any support film or membrane provides a backgroundsignal that is most significant for the smallest objects underinvestigation. Individual nanoscale particles or molecules usually needto be supported by a continuous membrane, as only tubular or rod-shapednanoparticles (such as carbon nanotubes) can be suspended across holesin the membrane. Indeed, single-walled carbon nanotubes (SWNTs) havebeen utilized for low-background TEM studies of encapsulated moleculesor defects in the cylinder-shaped graphene sheets. However, the limitedspace, harsh filling procedures, and strongly curved shape of the sheetlimit the applicability and complicate the analysis.

As we demonstrate below, a graphene membrane provides the ultimatesample support for electron microscopy: with a thickness of only oneatom, it is the thinnest possible continuous material. This, togetherwith the low atomic number of its constituent atoms, results in aminimum in inelastic scattering contributions. Due to its crystallinenature, a graphene support membrane is either completely invisible or,if the graphene lattice is resolved by a very-high-resolutionmicroscope, its contribution to the imaging signal can be easilysubtracted. Graphene is also a good electrical conductor and thereforedisplays minimal charging effects from the electron beam. Remarkably, wefind that a graphene membrane enables single adatom sensitivity evenwhen using a common TEM that does not resolve a graphitic lattice.

Preparation of our free-standing graphene support membranes is describedin the supplementary information. In order to observe adsorbates at thesingle-atom level, the graphene support membrane must be exceptionallyclean. In contrast to an earlier graphene preparation method, taught inMeyer, J. C., et al., The structure of suspended graphene sheets,Nature, 446, 60-63 and in the supplementary information to thispublication (doi:11.0.1038/nature05545), our approach does not rely onelectron beam lithography and is simple enough to be reproducible in anybasic microscopy laboratory. In brief, we start with graphene cleavedonto a substrate using an adhesive tape. Graphene pieces are identifiedby optical microscopy, and subsequently transferred to Quantifoil™ TEMgrids. We use electron diffraction analysis as described in Meyer et al.to verify the presence of a single layer. FIG. 4 a shows a lowmagnification view of a graphene sheet suspended across the 1.3 μm holesof the perforated carbon foil, with a close-up shown in FIG. 4 b. Morethan 50% of the area on these graphene membranes appears exceptionallyclean, with no dramatic contrast in high-resolution TEM images (FIG. 4b). As we now demonstrate, however, these “clean” regions containindividual adatoms that are readily observable by TEM. Althoughindividual exposures can reveal useful data, a dramatic improvement inthe signal-to-noise ratio is achieved by summing multiple subsequentframes (corrected for sample drift), which effectively increases theexposure time beyond the dynamic range of the TEM CCD detector. Summingas few as 5 frames yields striking visual improvement with atomic-scalefeatures (including individual atoms) becoming readily apparent, andsumming 100 frames reduces the noise to below 0.12% (standard deviationin a relatively featureless region of the graphene membrane).

FIG. 5 a shows a TEM image in which an individual carbon atom, attachedto the graphene membrane, is identified by an arrow. We recorded eightconsecutive, essentially identical images to that of FIG. 5 a, (each asummation of 20 frames on the CCD), demonstrating that the carbon atomdid not adsorb or desorb during the time of exposure. To identify theadatom, image simulations were carried out using the electron atomicscattering factors of Doyle, P. A., et al., Relativistic hartree-fockx-ray and electron scattering factors, Acta Cyst. A, 24, 390 (1968) andPeng, L. M., Electron atomic scattering factors and scatteringpotentials of crystals. Micron, 30, 625 (1999) for carbon, as shown inFIG. 5 b. The good agreement between the TEM data and image simulationconfirms the carbon atom identification.

Closer inspection of FIG. 5.a indicates not only additional similarcarbon adatoms, but also faint atomic-scale structure distinctlydifferent from carbon adatoms. To highlight these faint features, weshow in FIG. 5 d a summation of 100 consecutive TEM frames for the samephysical region. In this representation the carbon adatoms display sharpcontrast at the saturation of the gray level scale. FIG. 5 d reveals amoderate density of additional dark features (dark gray points, aselection of which are identified with red arrows) with identicalintensity profiles, all with a central dip reduction near 0.6% of themean bright-field intensity (FIG. 5 e). By comparing the TEM image datafor these additional features to adatom simulations, we rule out anyadatom heavier than helium, as well as a substitution of carbon atoms inthe graphene membrane by other elements. However, a hydrogen adatom,based on the electron scattering factors of Peng (referenced aboveresults in precisely the correct 0.6% dip in the bright-field intensity,shown by the red curve in FIG. 5 e. The large number of essentiallyidentical adatom profiles, along with the excellent agreement with thesimulated contrast, provides convincing evidence that we have, for thefirst time, detected individual hydrogen atoms by transmission electronmicroscopy.

In addition to individual adatoms, we observe by the same TEM imagingmethods the generation (by the electron beam) and dynamics of defects(vacancies) in the graphene membrane, as well as the dynamics of avariety of molecular-scale adsorbates. The formation of vacancies due toknock-on damage by the electron beam is shown in FIGS. 6 a-c. We alsoobserve vacancies that disappear by interaction with mobile adsorbates.Larger adsorbates (small molecules) become trapped preferentially atdefects, and can be observed at one position for typically one to fiveminutes. Frequently, we see that the vacancy disappears along with thetrapped adsorbate (FIG. 6 d-f), and the missing carbon atom hasobviously been resubstituted from the adsorbate. Further, we candirectly observe linear molecules on graphene membranes (FIG. 7) thatresemble an individual alkane or alkene carbon chain. These moleculesare found to spontaneously appear in the field of view, presumablyadsorbed onto the graphene membrane from the vacuum contamination. Wecan follow their dynamics for a few minutes until they decompose in theelectron beam, as shown in FIG. 7 b-d.

The remarkable TEM imaging capability afforded by a suspended, singlegraphene membrane warrants further discussion. For an ideal graphenesheet, there are no components in the structure with a period largerthan 2.1 Å, which is beyond the information limit of approximately 2.9 Åfor the microscope used in the present studies (JEOL 2010 operated at100 kV). Therefore, although the ideal graphene membrane cannot beresolved under these conditions, any perturbation to the crystallinestructure can be detected as long as a sufficient number of electronscan be recorded for statistical significance. Indeed, our graphenemembranes are highly stable in the electron beam at 100 kV, allowinglong data collection times on one region. For example, all images inFIGS. 5-7 are recorded from graphene membranes after between one andthree hours of irradiation (at ca. 7 A/cm2). Moreover, the summation of100 consecutive CCD frames corresponds to an exposure time of 20minutes, and distortions in the membrane during this time are below theresolution limit. This combination of a crystalline, atomically thinmembrane along with the high beam stability and the absence of anamorphous background signal on the nominally clean membrane enable thisunprecedented single-light-atom sensitivity in TEM. In comparison,single-walled carbon nanotubes (SWNTs) show strong deformations underthe same dose and energy of electron irradiation, probably because thecylindrical geometry allows beam-induced defects to relax via localdeformations more easily.

The observation of stable and well-localized hydrogen adatoms ongraphene, in spite of the irradiation and room temperature conditions,imply that these are chemisorbed rather than physisorbed atoms. Strongbonding of hydrogen to graphite is possible if the nearest carbon atomchanges its bonds from sp2 to sp3 configuration, with the carbon atomdisplaced from the plane by about 0.36 Å (FIG. 5 f). Moreover, it wasfound that hydrogen cannot bind to graphene if the carbon is confined toa plane (e.g. by strong bonding to a substrate), while an isolatedmembrane can deform easily to accommodate different types of bonds. Fromthe observed density of hydrogen adatoms, we conclude that only about0.3% of the carbon atoms in the graphene membrane are in an sp3configuration with a hydrogen adatom.

Our real-time observation of molecular dynamics has importantimplications for chemical diffusion and reaction dynamics studies. Asdemonstrated above, a variety of molecular scale adsorbates becometrapped on the membrane, and often detach again or decompose after a fewminutes. We can observe individual alkane-type molecules and we can evenfollow their migration. Observing this kind of molecule in the TEM hasimportant implications because it represents an essential ingredient oforganic chemistry. It therefore appears likely that other, more complex,molecules can be observed after deposition on graphene membranes. Wefind that the carbon chains are sufficiently stable and localized forcharacterization even at room temperature, and note that theseadsorbates were only trapped on the membrane after a moderate density ofdefects had been created by irradiation.

In conclusion, we have demonstrated that graphene membranes enable a TEMvisualization of ultra-low contrast objects. The imaging of individualhydrogen and carbon adatoms and carbon chains demonstrates a new levelof sensitivity that is relevant for organic materials. A key strength ofthe TEM is its ability to image individual entities rather thanaveraging over an ensemble, and direct imaging promises insights rangingfrom the characterization of complex chemicals and nanomaterials tobiological molecules. The extremely high sensitivity that a graphenemembrane in the transmission electron microscope provides with respectto adsorbates has allowed us to detect even hydrogen, demonstrating theultimate in TEM atomic sensitivity. While the study of defects,vacancies and edges of the graphene sheet itself will provide insightsfor potential electronic modifications of this new material, theplacement of objects on graphene membranes will enable unprecedentedanalysis by TEM, including electron spectroscopic analysis, and thestudy of molecular dynamics.

While the present invention has been described with reference to thespecific embodiments thereof, it should be understood by those skilledin the art that various changes may be made and equivalents may besubstituted without departing from the true spirit and scope of theinvention. In addition, many modifications may be made to adapt aparticular situation, material, composition of matter, process, processstep or steps, to the objective, spirit and scope of the presentinvention. All such modifications are intended to be within the scope ofthe claims appended hereto.

1. A method of suspending a graphene membrane on a support structure comprising: attaching graphene to a substrate; attaching a pre-fabricated support structure having the gap to the graphene; separating the graphene and the pre-fabricated support structure from the substrate which leaves the graphene membrane suspended on the pre-fabricated support structure.
 2. The method of claim 1 further comprising separating the graphene from bulk graphite prior to attaching the graphene to the substrate.
 3. The method of claim 1 wherein attaching the pre-fabricated support structure comprises: placing a pre-fabricated support structure having the gap on the graphene; immersing the pre-fabricated support structure and the graphene in a solvent; and evaporating the solvent which attaches the pre-fabricated support structure to the graphene.
 4. The method of claim 1 wherein attaching the graphene to the substrate comprises attaching the graphene to a sacrificial surface of the substrate.
 5. The method of claim 4 separating the graphene and the pre-fabricated support structure from the substrate comprises etching the sacrificial surface by immersing the sacrificial surface and the graphene in an etch solution.
 6. The method of claim 5 wherein the sacrificial surface comprises silicon dioxide.
 7. The method of claim 6 wherein the etch solution comprises potassium hydroxide.
 8. The method of claim 5 wherein the sacrificial surface comprises polymethyl methacrylate.
 9. The method of claim 8 wherein the etch solution comprises an organic solvent.
 10. The method of claim 9 wherein the organic solvent is selected from the group consisting of acetone and methylpyrrolidone.
 11. The method of claim 1 wherein separating the graphene and the pre-fabricated support structure from the substrate comprises placing a solvent adjacent to an edge of the pre-fabricated support structure which expands beneath the pre-fabricated support structure and the graphene and which causes the pre-fabricated support structure with the graphene membrane suspended across the gap to release from the substrate.
 12. The method of claim 1 wherein attaching the pre-fabricated support structure to the graphene comprises: applying an adhesive to a surface of the pre-fabricated support structure; and bringing the adhesive into contact with the graphene.
 13. The method of claim 12 wherein separating the graphene and the pre-fabricated support structure from the substrate comprises pulling the pre-fabricated support structure which leaves the graphene attached to the pre-fabricated support structure by the adhesive.
 14. The method of claim 13 further comprising immersing the graphene and the pr-fabricated support structure in a solvent which removes excess adhesive.
 15. The method of claim 1 further comprising heating the pre-fabricated support structure having the graphene membrane suspended across the gap after separating the pre-fabricated support structure and the graphene membrane from the substrate.
 16. The method of claim 1 wherein the pre-fabricated support structure comprises a TEM grid.
 17. The method of claim 1 wherein: the pre-fabricated support structure comprises a plurality of gaps; and separating the graphene and the pre-fabricated support structure from the substrate leaves the graphene membrane suspended across at least two of the gaps in the pre-fabricated support structure.
 18. The method of claim 1 wherein attaching the pre-fabricated support structure to the graphene further comprises attaching the pre-fabricated support structure to the substrate beyond where the pre-fabricated support structure attaches to the graphene.
 19. A method of depositing material comprising; placing a support structure having a graphene membrane suspended on said support structure under vacuum; adsorbing a precursor to a surface of the graphene membrane; and exposing a portion of the graphene membrane to a focused electron beam which deposits a material from the precursor onto the graphene membrane.
 20. The method of claim 19 wherein adsorbing the precursor to the surface of the graphene membrane takes place prior to, while, or after placing the support structure having the graphene membrane under the vacuum.
 21. The method of claim 19 wherein exposing the portion of the graphene membrane to the focused electron beam deposits amorphous carbon onto the graphene membrane.
 22. The method of claim 19 wherein exposing the portion of the graphene membrane to the focused electron beam deposits a dopant onto the graphene membrane.
 23. The method of claim 19 further comprising raster scanning the electron beam across the graphene membrane to produce a pattern of the material on the graphene membrane.
 24. The method of claim 23 wherein the pattern forms an electronic device on the graphene membrane.
 25. The method of claim 23 wherein the pattern forms a plurality of local perturbations on a nanometer scale.
 26. The method of claim 23 wherein the pattern forms an etch mask for further processing of the graphene membrane.
 27. An graphene-based structure comprising: a support structure having a gap; a graphene membrane suspended on said support structure; and a material deposited in a pattern on the graphene membrane.
 28. The method of claim 27 wherein the material comprises amorphous carbon.
 29. The method of claim 27 wherein the pattern comprises a feature dimension of less than about 2.5 nm. 